Ultrafast Dynamics of Sb-Corroles: A Combined Vis-Pump Supercontinuum Probe and Broadband Fluorescence Up-Conversion Study

Molecules. 2017 Jul 13;22(7):1174. doi: 10.3390/molecules22071174.

Abstract

Corroles are a developing class of tetrapyrrole-based molecules with significant chemical potential and relatively unexplored photophysical properties. We combined femtosecond broadband fluorescence up-conversion and fs broadband Vis-pump Vis-probe spectroscopy to comprehensively characterize the photoreaction of 5,10,15-tris-pentafluorophenyl-corrolato-antimony(V)-trans-difluoride (Sb-tpfc-F₂). Upon fs Soret band excitation at ~400 nm, the energy relaxed almost completely to Q band electronic excited states with a time constant of 500 ± 100 fs; this is evident from the decay of Soret band fluorescence at around 430 nm and the rise time of Q band fluorescence, as well as from Q band stimulated emission signals at 600 and 650 nm with the same time constant. Relaxation processes on a time scale of 10 and 20 ps were observed in the fluorescence and absorption signals. Triplet formation showed a time constant of 400 ps, with an intersystem crossing yield from the Q band to the triplet manifold of between 95% and 99%. This efficient triplet formation is due to the spin-orbit coupling of the antimony ion.

Keywords: corrole dynamics; femtosecond spectroscopy; fluorescence up-conversion; intersystem crossing; photoreaction; tetrapyrrole; triplet formation; ultrafast relaxation.

MeSH terms

  • Antimony / chemistry*
  • Fluorescence
  • Light
  • Porphyrins / chemistry*
  • Quantum Theory
  • Tetrapyrroles / chemistry*

Substances

  • Porphyrins
  • Tetrapyrroles
  • corrole
  • Antimony